EP0897388A1 - Siliciumfunktionlisiertes cyclopentadien - Google Patents
Siliciumfunktionlisiertes cyclopentadienInfo
- Publication number
- EP0897388A1 EP0897388A1 EP97919744A EP97919744A EP0897388A1 EP 0897388 A1 EP0897388 A1 EP 0897388A1 EP 97919744 A EP97919744 A EP 97919744A EP 97919744 A EP97919744 A EP 97919744A EP 0897388 A1 EP0897388 A1 EP 0897388A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cyclopentadiene
- silicon
- functional
- hal
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 15
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 12
- 150000003624 transition metals Chemical class 0.000 claims abstract description 12
- 150000001450 anions Chemical class 0.000 claims abstract description 10
- 239000003446 ligand Substances 0.000 claims abstract description 7
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 4
- 125000001424 substituent group Chemical group 0.000 claims description 15
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 230000000737 periodic effect Effects 0.000 claims description 8
- -1 alkalimetal amide Chemical class 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 239000004711 α-olefin Substances 0.000 claims description 5
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 claims description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 2
- KXYGKDBONOVZOM-UHFFFAOYSA-N 1h-cyclopenta[a]naphthalene Chemical compound C1=CC=CC2=C3CC=CC3=CC=C21 KXYGKDBONOVZOM-UHFFFAOYSA-N 0.000 claims 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- 125000005842 heteroatom Chemical group 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000002879 Lewis base Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- SJEUCMAOSGSDFY-UHFFFAOYSA-N chloromethyl-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane Chemical compound CC1=C(C)C(C)=C(C)C1[Si](C)(C)CCl SJEUCMAOSGSDFY-UHFFFAOYSA-N 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229940100198 alkylating agent Drugs 0.000 description 2
- 239000002168 alkylating agent Substances 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- VNPQQEYMXYCAEZ-UHFFFAOYSA-N 1,2,3,4-tetramethylcyclopenta-1,3-diene Chemical compound CC1=C(C)C(C)=C(C)C1 VNPQQEYMXYCAEZ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- UFERIGCCDYCZLN-UHFFFAOYSA-N 3a,4,7,7a-tetrahydro-1h-indene Chemical compound C1C=CCC2CC=CC21 UFERIGCCDYCZLN-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- JJGPPKDJWUKCJP-UHFFFAOYSA-N N-butyl-N-dimethylsilylbutan-1-amine Chemical compound CCCCN([SiH](C)C)CCCC JJGPPKDJWUKCJP-UHFFFAOYSA-N 0.000 description 1
- SQIKBMFZMZLSMO-UHFFFAOYSA-N N-dimethylsilyl-N-propan-2-ylpropan-2-amine Chemical compound CC(C)N(C(C)C)[SiH](C)C SQIKBMFZMZLSMO-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- PAJFATIYVLZNFC-UHFFFAOYSA-N chloromethyl(dimethyl)silicon Chemical compound C[Si](C)CCl PAJFATIYVLZNFC-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ANEFWEBMQHRDLH-UHFFFAOYSA-N tris(2,3,4,5,6-pentafluorophenyl) borate Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1OB(OC=1C(=C(F)C(F)=C(F)C=1F)F)OC1=C(F)C(F)=C(F)C(F)=C1F ANEFWEBMQHRDLH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/0827—Syntheses with formation of a Si-C bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0896—Compounds with a Si-H linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/6192—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
Definitions
- the invention relates to a process for the functionalization of a substituted cyclopentadiene; the invention also relates to a silicon-functional cyclopentadiene, as well as to a silicon- and amine- functional cyclopentadiene. The invention further relates to transition metal complexes derived from these and catalyst systems derived from these.
- a process for the functionalization of a cyclopentadiene, which is either ring-substituted or not, is known from an article by Jutzi et al. in Synthesis, July 1993, pp. 684-6.
- a hydrogen atom is abstracted from the cyclopentadiene under the influence of a Br ⁇ nsted base, resulting in formation of the corresponding anion.
- Br ⁇ nsted base can be used hydroxide (such as NaOH, KOH), hydrides (such as KH) , alkylalkali-metal compounds (such as the Li-alkyls, for example n- butyllithium) .
- the anion thus obtained is subseguently treated with an alkylating agent.
- the process is characterized in that the substituted cyclopentadiene is reacted with a Br ⁇ nsted base, after which the anion obtained is reacted with a dihaloalkylsilicon compound of the following formula:
- R 1 -R 4 each a hydrogen or a substituted or unsubstituted alkyl, aryl or aralkyl group
- M (earth-)alkali metal chosen from group 1 or 2 of the Periodic System of the Elements
- R 5 , R 6 each a hydrogen or a substituted or unsubstituted alkyl, aryl or aralkyl group - -
- the substituents R L -R 6 present in formulas (I)-(V) are a hydrogen group or a substituted or unsubstituted alkyl, aryl or aralkyl group.
- the Hal group in formulas (I), (II) and (III) is a halogen group from group 17 of the Periodic System of the Elements.
- the Hal group preferably is a Cl group; this enhances the reactivity of compound (II) in subsequent reactions.
- the cyciopentadienyl group (the -group) represented in formula (II) is ring-substituted with at least one substituent Y.
- the cyciopentadienyl group in formulas IV and V may also be ring-substituted with 1-4 substituents Y.
- Suitable substituents here are alkyl, aryl and aralkyl groups. By preference, alkyl groups are present as substituents. Such substituents may also form part of a ring system, such as occurs for instance in cyclopentadiene derivatives derived from indene, tetrahydroindene, fluorene and similar compounds.
- substituents are methyl, ethyl, propyl, isopropyl, n-butyl, i-butyl, t-butyl, phenyl, benzyl, cyclohexyl, trimethylsilyl.
- the cyclopentadiene can also be a heterocyclopentadiene.
- heterocyclopentadiene compound refers to a compound which is derived from cyclopentadiene but in which at least one of the C atoms in the 5-ring thereof has been replaced by a hetero atom, while the hetero atom has been selected from group 14, 15 or 16 of the Periodic System of the Elements.
- hetero atoms can be either identical or different. More preferably, the hetero atom is selected from group 15, especially preferably the hetero atom is phosphorus.
- the conversion of the suibstituted cyclopentadiene started from takes place under the influence of a Br ⁇ nsted base, which abstracts a hydrogen atom from the cyclopentadiene and so produces an anion.
- a lithiumalkyl compound more preferably n-butyllithium, is used for this purpose. With these compounds the anion is formed very fast and selectively. The anion is subsequently contacted with the dihaloalkylsilicon compound of formula (I). - -
- Both the formation of the anion and the reaction with compound (I) normally take place in a solvent.
- Suitable solvents are those substances in which both the starting product and the reaction product are soluble.
- Hydrocarbons for instance hexane or pentane, or ethers can be used.
- a compound having Lewis base characteristics is chosen; this promotes the H abstraction.
- Ethers in particular are suitable for this, weak Lewis base ethers (i.e. bases the conjugated acid of which has a pKa value ⁇ -2.5, such as dimethoxyethane, diethyl ether and dioxane), as well as, most preferably, strong Lewis base ethers (such as tetrahydrofuran (THF) having a corresponding pKa value of -2.0).
- weak Lewis base ethers i.e. bases the conjugated acid of which has a pKa value ⁇ -2.5, such as dimethoxyethane, diethyl ether and dioxane
- strong Lewis base ethers such as tetrahydrofuran (THF) having a corresponding pKa value of -2.0.
- the temperature at which the formation of (II) and (IV) takes place is usually between -40 and +50°C; preferably the reaction temperature is between 10 and 35°C.
- the pressure at which the reactions are carried out is not critical; atmospheric pressure is already sufficient.
- the silicon-functional cyclopentadienes according to the invention are suitable for a wide variety of applications. They are suitable in particular to be incorporated in a transition metal complex of a transition metal and one or more ligands on the basis of a cyclopentadiene.
- Suitable cyclopentadiene ligands are one or more of the above- mentioned silicon-functional cyclopentadienes according to the invention. This applies in particular if such a transition metal complex is used as a catalyst in a catalyst system for the polymerization of ⁇ -olefins, with the catalyst system also comprising a cocatalyst. In such a situation the transition metal in the complex has been chosen from groups 3-6 of the Periodic System of the Elements.
- the invention therefore also relates to a process for the polymerization of an ⁇ -olefin with the aid of a catalyst system of the type indicated above.
- the polymerization of ⁇ -olefins for example ethene, propene, butene, hexene, octene and mixtures thereof and combinations with dienes, can be carried out in the presence of the metal complexes with the cyciopentadienyl compounds according to the invention as ligand.
- Suitable in particular for this purpose are complexes of transition metals which are not in their highest valency state, in which just one of the cyciopentadienyl compounds according to the invention is present as ligand and in which the metal is cationic during the polymerization.
- Said polymerizations can be carried out in the manner known for the purpose and the use of the metal complexes as catalyst component does not make any essential adaptation of these processes necessary.
- the known polymerizations are carried out in suspension, solution, emulsion, gas phase or as bulk polymerization.
- the cocatalyst usually applied is an organometal compound, the metal being chosen from - -
- alkylaluminium alkylaluminium halides, alkylaluminooxanes (such as methylaluminoxanes) , tris(pentafluorophenyl) borate, dimethylanilinium tetra(pentafluorophenyl) borate or mixtures thereof.
- the polymerizations are carried out at temperatures between -50°C and +350°C, more particularly between 25 and 250°C.
- the pressures used are generally between atmospheric pressure and 250 MPa, for bulk polymerizations more particularly between 50 and 250 MPa, and for the other polymerization processes between 0.5 and 25 MPa.
- dispersants and solvents use may be made of, for example, hydrocarbons, such as pentane, heptane and mixtures thereof. Aromatic, optionally perfluorinated hydrocarbons, are also suitable.
- the monomer applied in the polymerization can also be used as dispersant or solvent.
- Example II was repeated, starting from 1.75 g (13.5 mmol) of di-n-butylamine and 3.05 g of (1,2, 3,4- tetramethyleyelopentadien-5- yl)chloromethyldimethylsilane (13.3 mmol). GC analysis showed 100% conversion. After evaporation 3.95 g of (1,2,3 ,4-tetramethylcyclopentadien-5-methylyl) ( N,N-di- n-butylamino)dimethylsilane was obtained.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL1003002 | 1996-05-03 | ||
| NL1003002A NL1003002C2 (nl) | 1996-05-03 | 1996-05-03 | Siliciumfunctioneel cyclopentadieen. |
| PCT/NL1997/000224 WO1997042196A1 (en) | 1996-05-03 | 1997-04-25 | Silicon-functional cyclopentadiene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0897388A1 true EP0897388A1 (de) | 1999-02-24 |
Family
ID=19762773
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP97919744A Withdrawn EP0897388A1 (de) | 1996-05-03 | 1997-04-25 | Siliciumfunktionlisiertes cyclopentadien |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0897388A1 (de) |
| JP (1) | JP2000510831A (de) |
| AU (1) | AU2410197A (de) |
| NL (1) | NL1003002C2 (de) |
| WO (1) | WO1997042196A1 (de) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0256981B1 (de) * | 1986-08-01 | 1993-02-17 | Ciba-Geigy Ag | Titanocene und deren Verwendung |
| JP2795474B2 (ja) * | 1989-07-27 | 1998-09-10 | 三井化学株式会社 | オレフィン重合用触媒成分およびオレフィン重合用触媒ならびにオレフィンの重合方法 |
| JP3341117B2 (ja) * | 1991-10-15 | 2002-11-05 | ザ ダウ ケミカル カンパニー | 金属配位錯体の製造 |
| ES2150653T3 (es) * | 1995-02-24 | 2000-12-01 | Novartis Ag | Ferrocenildifosfinas sililadas, ferrocenildifosfinas sililadas unidas a soportes inorganicos o polimeros organicos, asi como complejos metalicos de estas, su obtencion y empleo. |
-
1996
- 1996-05-03 NL NL1003002A patent/NL1003002C2/nl not_active IP Right Cessation
-
1997
- 1997-04-25 EP EP97919744A patent/EP0897388A1/de not_active Withdrawn
- 1997-04-25 AU AU24101/97A patent/AU2410197A/en not_active Abandoned
- 1997-04-25 JP JP09539778A patent/JP2000510831A/ja active Pending
- 1997-04-25 WO PCT/NL1997/000224 patent/WO1997042196A1/en not_active Application Discontinuation
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9742196A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2410197A (en) | 1997-11-26 |
| JP2000510831A (ja) | 2000-08-22 |
| WO1997042196A1 (en) | 1997-11-13 |
| NL1003002C2 (nl) | 1997-11-06 |
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